Processes of adsorption and of electron beam induced desorption of water at aluminium single crystal (100) have been investigated simultaneously using the techniques of Electron Stimulated Desorption (ESD) and of Auger Electron Spectroscopy (AES). The predominant ion production with ESD is H + and OH + ions with, respectively, kinetic energies of around 4.9 and 1.8 eV, and with desorption efficiencies (maxima) of 1×10 −5 and 2×10 −7 ion/electron. The behavior of these ion signals in the initial region of gas exposure (<10 L) at the clean surface is complex - the yield of OH + ions, for example, passes through a maximum at an exposure of around 4 L. Both ions are identified as arising from OH groups at the surface, and the findings, corroborated by the observations with AES, are identified with the transformation of an initial chemisorbed phase to an oxide surface. The kinetics of adsorption, both in the initial chemisorbed phase and with the evolution of oxide, are shown to support an island growth model. The desorption induced by electron impact has similarly been monitored by the two techniques. The technique of ESD is far more responsive to the action of electron beams, and this is attributed to its greater sensitivity to the topmost surface layers. Both techniques contribute to the finding of a process of oxidation induced by electron bombardment.